Sterilization and clarification of raw waters



llanldldlamlrynllawnmamlgneeterhih delphhqurtlfiemne v earpelatiouaflennlylvl may , NaDrawin. AM -Imflm SE NO. man

1 Thhinvmiionrelatestosterllilationandclariiieationofrawwaternanditeomprisaamethodofelarifyinsandpm'lfy lrawwatemfor potablemrpoeesforexample.whereinaeo'aularmeaddedraneinspteferablyfromaboutonto 2.0molspermolofNaa0presentinthesilieate solution. the resulting coagulation aid beins then to usually aged approximately to the pointo! ineipient gel formation and advantageously diluted before beins added to usualeoasulants. Theinventionalsoineludes 1s thept'oeessofformilmthetleeei'ibedeoagulutionaids;allasmorefullyhereinaftersetforth andas' Beveralwatetpurifleationhavebeen. developedwithinthepestfewyearsmakinsme a coagulation aid formed by addins sulfuric acid to a sodium silicate solution to a point somewhat shortotneutralhatiemfollowedbyes ltosu pointshortofgelationandthendilutiontoprodueestahilization. Aseeondproeasinvolves the monimnsalts tionaid. Itisevidentthateaehoftheseproe- 35 agulants. 'l'hereisaneseeptiontothisinthe 4o easeofinstallationsmaklnsuseottheehloramine process of water. in wh we the 'sulfate.ususllyempl0y inmakins theohloraminemanbemadetoperformthedoublefunetionofreaetinswiththesodiumsilieaie toformthedeeimdeoexulltionaidandalsoof rodueinstheehiorammeiasdeseribedinmy aeknowlelkeda pplieation. mmyapplieatinntbem mentionedotpuothteinlaeoasulatimaidhyreso 1 Chill.- (Cl- 210-33) acting chlorine with a mum silicate solution inwiththefolluwinleq l 'nmo-aassioa+ch=uaoci+aassioi+mcl V NaOCl+Ch+HsO=2KOCl+NaCl Ihavefoundthatthepraetiealuseofthismw coagulation aid results in several surptisinzand hishly valuable results.

I have found. for example. that, in water purifyinz installations 'employin: the conventional pre-ehlorination step. the chlorine used in this step can be employed in making In! m tlon aid. with the pre-ehlorination step being elimitherawwaterbeforeitpaseeeintd orsettlinahasin. One'ofitspmpoeeslstoster'ilisetheiioewhieheventuallydepoeitsinthesettlinxbasim'ThisiioeJormedbytheadditionof mooagulatingchemlclll.lllchllalum.irdnsflts and/or lime. carries down-with it small animal lifesuehasmierobesandeysmmrembeeteria ete.whiehmaybepxeaentintherawwater alone with suspended organic and inorsanie matter. Thesettlinsofthei'loeprodueesaclariiiedwater. Butintheabseneeofthepre-ehlorination step the settled mass frequently forms an active medium for the zrowth of bacteria and the putrefaetion of organio solids. The foul odors produoed thereby may contribute a distasteful factortothepurliiedwatetatleastatoertain seasons, and gases given of! may lid to re-suspend precipitated sediment. These conditions are alleviated by theme of a pre-ohlorination step..

rrequentlyinthoeeinstallationsinwhichtheoost is considered somewhat too high to justify the use 0! a pre-ehlorination step. the introduction of such a step would produce an appreciable improvement in the taste and odor of the clear water. sineetheuseofmyneweoagulationaid performs all the sterilizins functions of a preehlorinatlng step. it is therefore evident that my process is valuable even in installations which ordinarily do not employ pre-ehlorimtion.

I have found. surprisinslv. that when the chlorine used in a pie-chlorination step is employedinthemakiusofaeoasulationmsubstantially in accordance with the above equations. the sterllisinl eifeet produced upon the subsequent addition of the eoalulltion aid to possiblethatthischlorinetrappedin the flocs as they form,

resulting in a more thorough sterilization thereof.

Second,itispossible thatthemicellaofhydroussilicahinderthe escapeoithechlorinetromthetreatedwater. Ihavenotedthattheflomwhicharetormed in myprocessai'tertheadditionotthecoagulation aid and the coagulant, frequently have minute bubbles of gasattached thereto, especially when 'the quantity oi chlorine used in making the aid is close to the upper end or the operative range.

These bubbles are presumably either chlorine or possibly ongen resulting from the decomposition of the hypochlorite formed in the process. The fact that these bubblu tormpn the flocs may tend to delay their escape from the water. Third. thesilicainthecoagulation aidma serve'to stabilize and prevent decomposition of the sodium hypochlorite or hypochlor'ous acid formed in the process. possibly by removing or preventing the catalytic action at metal salts or other materials present in the'water. But whatever the true explanationmay be, the fact remains that the sterilizingactionoi'thechlorineisusuallyenhancedwhemitisusedinmakingmycoagmation aidlbeio're being added to the water.

In view 01' the or increased sterilizing action or the chlorine used in productionotmycoagulation aid.itisevidentthatin any water purifying installatmns employing a lire-chlorination step. the cost 01 the chlorine usedinmaking-theaidcanbeentirelywrltten 01!. And. since the addition of my'coagulation aid reduces the quantity oi, chlorine required in the flnal chlorinating step, it is evident that this cost can be largely written oil even in them installations in which no pre-chlorination step is generally used.

Another unexpected discovery is that the residual chlorine or raw water treatedwith my iilter aid is not dissipated as rapidly'as stances. The effect is' somewhat like that ohtainedbytheuseofthechloraminetreatmentin oomparisonwith the use of chlorine alone. The so-ealled dead-end troubles are reduced and the growth of bacteria and algae. such 'asastcrionella (which produces a fishy odor) and crenothrlx (which produces a very oil'ensive decayed odor or taste in storage) is retarded or eliminated.

A still further surprising result obtained in my is that flocculation is improved in comparison with the results obtained with the coasulation aid iormed'by the addition 01' sulfuric acid to a sodium silicate solution The speed of lormationci'theflocisandthesiae oi'the floc formed is greater. 'lhisresultwas raw water in the same way as priorart,thatis.prlortotheentrance waterintoacoagmathnorsettl'ingbasin eitherbefore or after the addition 01 coagulants usedin the process. I usually to add the aid prior to-the coagulant when the aid in conjunction with clarlflcationor color and/or turbidity, after the coagulant.

8 1- Aft r 8111:, unless promptly to the raw water, it to extend its life. This dilution least sumcient to produce a concentra exceedingaboutlpercentbyweight. Oteourse'. the smaller this dilution the analler the tank muired'buttheshorter the lite ot the inmakingtheaidandaddingittotheraww supper-limit of chlorine addition ter, it is usually not to diluteit, although. of courser dilution can also he accomplished continuously, if desired. i

It is advantageous to add suillcient chlorine to the silicate solution so that the molecular ratio of C1: to NazO is at least about 0.7 to l. "l'he several factors; The gel induction periods of my n18 point Imis and toLthe'gelhiductionperiomincreasetothe' before gelation of by ore-chlorination. It is also coagulation aid has an im-.

which is in contrast 7 a sodium nets of the initial An aid in which added per mol of NasO, about'225 weight percent. for example. has a life only about represents about the minimum practical gel induction period to employ. The pH of the coagulation aids, as determined with the glass electrodemd for example. may vary between about 11 In comparison. in the case of the coagulation aid produced by the addition of sulfuric acid to silicate solution. the latter can not be neutralized beyond about 85 per cent at concentrations higher than 1.5 per cent by weight of SlOa, since otherwise gel formation is likely to occur before dilution can be effected. For best resultsthealkalinityof thisaidmustlie between the narrow limits of 1150 to 1250. It will be noted that, in the production of my new aid this close control is not required. which is an important advantage. This results because one of the prodneutralization is an alkaline salt. My aid can be prepared at a substantially lower pH than is possible in the case of other aids. 1

It is evident from the above description that my process-combines the two steps of pre-chlorination and the use of a coagul tion aid withducedbytakingwpartsby metbodinaohialpraetiee.

. laliltplel A standard mics-story eiarifleatiui test was conducteduponaraw'watermadebyadding mflicientinertclaytociiy tap'watcrto produce ahirbidityofooparmpermiilion. Theclsywas addedtoincreasetheaccuraeyoftbemeamrementofdocformation. Utersamplescfthls rawwaterweretreatcdinabeakereouippedwith astirrlngdevicemtatintfl'timesaminute.

Intheiirst'testthecoasulationaidwasprovolumeofasodium silicate solution j havlnu a weight ratio illaa0z3228i0: and an NasO concentration of 3.1 weight per cent. diluting it with 180 parts of water and then bubbling in chlorine until 99.5 centofthealkaliwasncutralimasshown bytitration with sodium thiosulfate. the addition of the chlorine taking 12 minutes. The resultingcoagulationaidwasaged foraperiodof65 minutes after which itwas'dilutedtoil percent 810:. Thisagedanddilutedcoagulationaid was addedto the raw waterinquantity sufficient toproduceSRRMJfSiOrintheIatterL Alum wasthenaddedintheamountoflORRM. The ilrstiiocappearedinljminutesandflocformm tion was complete in about 1.0. minutes. The

flocs formed were very large and heavy. settling within about Zniinutes after the stirrer was stopped.

comparative tests were made using alum alone. a coagulation aid produced by adding sulfuric acid to the same silicate solution and a coagulation aid produced by adding'alum to the silicate solution. It was found that none of these methods produced flocs as rapidly. as large or as quickly as in the case of my new coagulation aid. 'The comparative results obtained are colout elimination of the function of either step and. lected in the following table:

sm, 1 m Flocam Size, coagulant P. P. 1!. Appearance Complete Settling mm.

Nona (Alum alone) 8 g 'z'i 51m 1 i1. sda;:::::::::::::::: 4 ii i 3 L5 7.0 Excellent 8 in fact, with cut of the effect produced Example 2 evident that in my new process the portant auxiliary function. to other p aking use'of such aids.

Of course the optimum agin period. the optimum ratio of chlorine to silicate solution. the optimum concentrations of the solutions and the optimum quantity of the tobetreated. by the season of the optimum this quantity is within the range oi. i to 15 P. P. M. of $10,.

My invention can be described in somewhat mm:- detail by reference to the following 8P aid to be added to the raw waters. varies to some extent with the water is of course affected tion aid was aged for 16 minutes. corresponding indicated in Example 1.

to about 84 per cent of the solution life (gel induction period) after which it was diluted to 0.5 per cent silica. This aid was added to the raw water and then alum was added in the amounts In this test the first line formation was noted in 2 minutes. Floc formation was complete in 8 minutes and it required only 3 minutes for the iioc to settle after turned off. The results produced slightly inferior to those obtained in Example 1. In this test it wasnotcd that tinygasbubbiestendedtoformontheiiocand I 1 Tammie: Inthisexampleasolutionoi'thesamesilicate ,eonmmm 1.51m cent sios'wasneutralised to vtheextentofpercent,asdeterminedliytiti'acorresponds-teen endpointoffrom 12.6-12.8 ml. of a 0.18 sodium thiosulfate solutionmthstitrationofanacidiflediomLsample, usingapotaaiumiodide-starchsoluflonasindlcator Ao ulstionaidproducedinthis'manner has a solution lifeof from 24 to 30 hours at 20C. l"romonetotwohoursoftisingproduces asatisfactorycoagulationaid. Inthisparticular test the aid waslaged for 2 hours, then diluted omiy without gel formation taking A simpl way to conduct the addi oagulation 'aid with period is to provide silicate solution, having from about 0.5 to 15 mo wh s the state of incipient gel formation or to the a concentration ranging per cent by weight, for expoint'at which a sample of the chlorinated mix to 1 percent SiO: for

Upon addition to theme raw water it was found to produee excellent clarification with results comparabletothoseproducedinlixample 1.

trample l Inthis testa flow of river water amounting to live million gallons per day was treated. The coagulaflonaidwasnreparedandaddedcontinuousl by first diluting a sodium silicate solution, having a weight ratio of 1NasO:3.22SiOr. to

a concentration of 1.5 per cent 810:, adding chlorine from a-special chlorinator at the rate of 2.34 pounds per hour, thereby neutralizing about 95 per cent of the NasO. 81118 for a period of mlnutesidilutlng to 0.5 percent SiO: and then feeding this coagulation aid to the raw wateratarateSllliPlying4RRM. ofSiOain conjunction with a feed of alum amounting to 12 P. P. M. Excellent clarification was produced in this test, Substantially better than that produced dnacomparativetestusingacoagulationaid formed by partially neutralizing the same sodium silicate solution with sulfuric acid. The flocs formedwereverylargeandsettledrapidly. The sludgewas found to beeii'ectivelysterilized as well as the eiliuent water. I

WhileIhavedescribedwhatIconsidertobe the most advantageous embodiments of my process, it is evident, of course,-that many modificationscanbemadeinthe speciiicproceduresdescribed without departing from the purview of this invention. While I have mentioned the use of alum, (aluminum sulfate) iron salts and lime as coagulantstobeused in conjunction withmy coagulation aids. any oa ulating chemical.

which is capable of forming an insoluble precipitate when reacted with a sodium silicate solution, is applicable. As mentioned previously, in the one of some waters it is possible to dispense entirely with the us of coagulants in addition to my coagulation aid. It isalso possible in some cases to employ all the chlorine required for sterilirationpurposesinthemakingofmycoagul'ation aid. These procedures result, of course,

in a substantial simplification of the clarifying While I have indicated that using of my emu.

lation aids is usually required for best results,

le improvement in coagulation can be obtained when these aids are added to the raw water without special provision for an aging period, for example, in conjunction with lime softeninginwhichnoalumisused. 'I'heaidproduced in Example 3, for exampIe,-can b added directly to the water without aging and, if it is consumed before the endo! its induction period, thatis,beforegelation,itisnotn todilute cient size to provide a retention ,if allowed to a period of about? stand, will forma gel'within to 30 minutes, and then passingit into the rawwater. Agitation andchlorination can be accomplished either in av launder or may be of sumtime which would be a small fraction of the gel induction period.

When on. the batch basis the chlorine can be w into the silicate solution rather slowly so that the solution is aged when chlorination is completed." Completion of the chlorination can bedetermined I following the increase inviscosity, by measuring the jail or by atank. Ifatank-isusedthis .casestheproperamounttobeaddedisthatrm quiredtocausetheformationofasilicasol-which hasatendencytogelaiteraninductionperiodof from about 3 minutes to 300 hours. As stated previously this silica sol is advantageously used to the point of incipient gel formation or for a period representing from about 1 to 90 per-cent of the induction period. following which-the aid is either added directly to the raw water or is diluted for stabilization prior tobeing added to the water.,lngeneralitcanbesaidthat,themore dilute the silicate solutionth more chlorine required to produce the coagulation aid, and vice versa. For example, a silicate solution having a concentration of from about 5 toper cent SiOr would require neutralization only to about per cent, while in the other direction a silicate solu tion having a concentration of only 0.3 percent thbsldtostabiliseit. Ineeectthednuuon" added in the form of a solution would require neutralization to the extent of from about 150 to 200 per cent. Up to the point of about percent neutralization. the addition of a small additional amount of chlorine is, in some respects, equivalent to the use of an aging period. that is, the additional chlorine shortens the gel induction period. If desired, the chlorine may be of hypochlorous acidorchlorine water.

It is believed that the above directions are sufllcient to enable anyone skilled in the water treating art to produce coagulation aids which would be eil'ective in the treatment of all natural waters which can be classed as ofthe common or usual type. 'This includes the treatment of sewage as well as industrial wastes, such as P per mill wastes, the precipitation of suspended pigments and other liquors. In practically all cases wherein hidustrial liquors are being clarified with andchlorinatingthisstreamto' determining the time required for subsequent gel ployed the chlorine by weight. 7

present suiflcient to produce ase'mes Other alkali metal silicateafsuch as potassium silicate, can be employed in place of sodium silicate in my invention but this is merely of academic interest owing to the high cost of other silicates. Other modifications of my fall within the scope of the following claims will be immediately evident to those skilled in this art.

What I claim is:

1. In the manufacture use in clarifying raw comprises adding suilicient chlorine to a dilute aqueous sodium silicate solution. having a weight ratio of N820 to 510: ranging from about 1:1 to 1:4 and a concentration of about 0.5 to 15 per cent by weight to produce a mixture-which is in the state of incipient gel formation, then diluting the solution with water to stabilize it and to prevent gel formation prior to use.

2. The process of lation aid is diluted by adding to be clarified.

3. The process of claim 1 is added until the molecular ratio of chlorine to. the N820 of the sodium silicate is within the range of about 0.7:1 to2.0:l.

4. The process of claim 1 wherein the sodium silicate solution after dilution has a concentration ranging from-about 0.3 to 5 per cent S:

it to a raw water 5. The process of claim 1 wherein chlorine is added until the mixture will form a gel, if permitted to stand; within a period of about 3 minutes to 300 hours.

' to per cent by weight. in quantity amounting to mols of Oh per mol of NaaO a mixture which can be aged to produce a state of incipient gel formafrom about 0.7 to.l.5

. tion aging the resulting mixture until it is in the state of incipient gel formation and diluting to prevent gel formation prior to use.

8. In the manufacture of coagulation aids for use in sterilizingand clarifying raw waters, the process which comprises adding chlorine to a dilute aqueous sodium silicate solution, having a ratio of NazO to SiO: within the range of about 1:1 to 1:4, and a concentration ranging from about 0.5 to 15 per cent by weight, the quantity of chlorine added being from about 0.7 to 1.5 mols per mol of NazO present sufllcient to produce a mixture'which can be aged to produce a state of incipient gel formation, aging the resulting mixture to the extent of about 1 to 95 per cent of its gel induction period and diiuting'with water to stabilize the resulting coagulation aid.

9. Inthe sterilization and clarification of raw waters,- the process which comprises adding to the raw water a small amount of a water soluble coagulant which is capable of forming an insoluble precipitate when reacted with a silicate solution and. prior to the coag ation, adding to the water a small amount of a coagulation aid formed by adding sufiicient chlorine to a dilute obtained 'with the use of mycoaguclaim 1 wherein the coagu-.

wherein the chlorine claim 1 wherein the silicate process which I waters, the process which coagulant required l aqueous sodium silicate solution, having a' ratio of Nero to 510: within the range of about 1:1 to i :4 and a concentration ranging from about 0.5 to

15 per cent by weight, to produce a mixture in the state of incipient gel formation, and removing the resulting precipitate from the water.

. 10. In the sterilization and clarification of raw waters, the process which comprises making a coagulation aid by adding chlorine to a dilute aquesilicate solution,rhaving a ratio of ranging from about 1:1 to 1:4 and cm sodium NazO to BiO:

a concentration ranging from about 0.5 to 15 per cent by weight, the amount of chlorine added amounting to from about 0.7 to 1.5 mols per mol of NazO present in the silicate solution and being sufficient to produce a tendency for the mixture to form a gel after a short induction period, then prior to the end of said induction period, diluting it to prevent gel formation, adding the resulting coagulation aid to the water and also adding any to produce saidcoagulant being one capable of forming an insoluble precipitate when reacted with a sodium sflicate solution, then removing the said iloc from the water.

11. The process of claim 10 wherein the mixture'is aged to an extent representing from about 2 to 10 per cent of said induction period.

12. In the process of sterilizing and clarifying raw waters, the process which comprises passing into a stream of raw water a stream of a dilute aqueous sodium silicate solution having a concentrationof from about 0.5 to 15 per cent by weight to which chlorine has been added in quantity sufficient, if the mixture were allowed to stand, to

a voluminous floc,

produce the formation of a gel within a period of from about 3 minutes to 300 hours, also adding any coagulant required to produce the formation of a voluminous floc, said coagulant being one selected from a class consisting of alum, aluminum sulfate, water soluble ironv salts and lime and capable of forming a precipitate with a sodium silicate solution, and separating the floc from the water.

13. In the process of sterilizing and clarifying raw waters, the process which comprises preparing a dilute aqueous sodium silicate solution havtakes place,

,tion to produce a precipitate and separating said precipitate from said water.

14. In the process of sterilizing and clarifying raw waters, the process which comprises forming a coagulation aid by adding chlorine to a dilute aqueous sodium silicate solution, having a ratio of NazO to 8102 within the range of about 1:1 to 1:4 and a concentration of from about 0.3 to 5 per cent SiOz by weight, the amount'of chlorine added'being from aboutilfl to 1.5 mols per mol of No.20 present, aging the resulting mixture for a period equal to from about 1 to per cent of its gelinduction period, diluting the aged mixture by adding sumclent water to stabilize it, adding the so-produced aged and stabilized coagulation aid to a raw water and also adding the formation -of whichileelected iromoclasa consisting of alum.

o voluminou flocculent precipitate, and remov-- lng eoid precipitete from the water. I L

mnomnm t. moms cn'm 'lbe following reference: are of record in the illeoi'thilpotent:

i: I I v V UNITED STATE PA'IIIITB Number Home I I Dote Lovie Nov. 8,1859 m I". 8, 1,27 Greenei: cl. Dec. 20. 192'! Johnson 4. Dec. 1, 1931 Salmon-metal. Mn. 11, 1941 v Relchelt cl; :1. June 28, 1942 Apr. 2'], 1943 Wohel Jan. 1 1944 King Bob. 27, 1945 King Feb. 27. 1945 

1. IN THE MANUFACTURE OF COAGULATION AIDS FOR USE IN CLARIFYING RAW WATERS, THE PROCESS WHICH COMPRISES ADDING SUFFICIENT CHLORINE TO A DILUTE AQUEOUS SODIUM SILICATE SOLUTION, HAVING A WEIGHT RATIO OF NA2O TO SIO2 RANGING FROM 1:1 TO 1:4 AND A CONCENTRATION OF ABOUT 0.5 TO 15 PER CENT BY WEIGHT TO PRODUCE A MIXTURE WHICH IS IN THE STATE OF INCIPIENT GEL FORMATION, THEN DILUTING THE SOLUTION WITH WATER TO STABILIZE IT AND TO PERVENT GEL FORMATION PRIOR TO USE. 